CA1045265A - Sulphur-bituminous compositions stabilized with organosiloxane polymer - Google Patents
Sulphur-bituminous compositions stabilized with organosiloxane polymerInfo
- Publication number
- CA1045265A CA1045265A CA240,696A CA240696A CA1045265A CA 1045265 A CA1045265 A CA 1045265A CA 240696 A CA240696 A CA 240696A CA 1045265 A CA1045265 A CA 1045265A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- sulphur
- bituminous material
- polymer
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
- C08L95/005—Aqueous compositions, e.g. emulsions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Road Paving Structures (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A small amount of an organosiloxane polymer stabilises an emulsion of sulphur and a bituminous material in which the bituminous material is a continuous phase and the sulphur is a dispersed phase; the stabilized emulsion serves as a binder for mineral aggregates in the manufacture of paving mixtures;
the polymer is suitably one having the general formula:
A small amount of an organosiloxane polymer stabilises an emulsion of sulphur and a bituminous material in which the bituminous material is a continuous phase and the sulphur is a dispersed phase; the stabilized emulsion serves as a binder for mineral aggregates in the manufacture of paving mixtures;
the polymer is suitably one having the general formula:
Description
The invention relates to a stabilized binding com-position for mlneral aggregates in the manufacture of paving mixtures, and its preparation, the invention is further concerned with paving compositions and their preparation, more especially the invention is concerned with compositions comprising emulsions of sulphur in bituminous materials for use as a binder for mineral aggregates in the manufacture of paving mixtures.
,`~ Compositions comprising sulphur emulsified in asphalt have been proposed as binders in paving compositions in U.S.
- Patent ~o. 2,182,837, however, such binders have not been used to any great extent. These prior binders are of low stability and it is necessary to use them without delay in making pavin:~
compositions, this necessitates manufacturing the binder at `~ the paving plant site, and this in turn requires the use of two mixers, a high shear mixer such as a colloid mill to form an emulsion of sulphur in asphalt, and a pugmill to mix-the minera' -X
aggregates and the emulslon.
,~ In view of the difficulties experienced when using asphalt-sulphur compositions and, until recently, the ready availability of asphalt at low cost, the industry has favoured the use of asphalt alone as a binder for aggregates in paving compositions.
The invention provides an improved binder composition : . . .
~3 having greater stability than the aforementioned prior binder compositions, in which the now readily available sulphur is employed in an emulsion with bituminous material thus reducing the quantity of the more expensive bituminous material employed ~ in the paving mixture. In addition, the invention provides a - 30 simple procedure for manufacturing such emulsions.
The invention further provides a method of manufactur-ing a paving composition which avoids the necessity of a ~,:. ~ ' ' .
~, , - . ~. ~
~045Z65 preliminary mixing operation to form a sulphur-bituminous emulsion.
; It has now been found that a small amount of an organo-siloxane polymer will stabilize an emulsion of sulphur and a bit-. . j uminous material.
According to the invention there is provided a stabilized binder composition for mineral aggregates in the manu-facture of paving mixtures comprising an emulsion of sulphur and a bituminous material and an emulsion stabilizing amount of an organosiloxane polymer in which said bituminous material is a . ~, continuous phase and said sulphur is a dispersed phase.
According to another aspect of the invention there is `~ provided a method of preparing a stabilized binder composition for ~, mineral aggregates in the manufacture of paving mixtures which com-prises mixing together at an elevated temperature bituminous mate-rial, molten sulphur and an emulsion stabilizing amount of a liquid organosiloxane polymer to form an emulsion having a continuous -~ phase of bituminous material and a dispersed phase of molten sul-,~ phur.
.:
In another aspect of the invention there is provided a method of manufacturing a paving composition comprising mineral 1, aggregates and the binder formulation of the inven~ion, which com-/' prises simultaneously mixing together, at an elevated temperature, liquid bituminous material, liquid sulphur, an emul~ion stabilizing amount of an organosiloxane polymer and a major aunt of a mineral aggregate; the sulphur being emulsified in ~ the bituminous material.
,~ In yet another aspect of the invention there is pro-vided a paving composition and a paved surface formed from ~' the paving composition.
In an embodiment of the invention a method is provided for the simple plugged flow blending of the bituminous material and sulphur just prior to the pugmill weight bucket, in cases ., ~ 2 -.','.,' ~ ~ . - '' 104SZ65 ; ~
.
where it is desirous to simplify the paving plant modifications necessary, to enable the binder compositions of the invention -. .
to be used to prepare paving compositions, and also to maintain the paving plant capacity.
In the emulsions of the invention, the liquid sulphur ~; - .
forms a discontinuous phase or dispersed phase in the continuous liquid bituminous phase.
Although the inventors do not wish to be limited to , any particular theory, it is thought that the stabilizing effect of the organosiloxane polymer on the sulphur-bituminous emulsion arises from the formation of an insoluble monolayer of the polymer at the liquid interface of the sulphur and bituminous ~$ material; the monolayer resulting in a significant reduction in the sedimentation rate of liquid sulphur particles during storage.
A further stabilizing of the sulphur-bituminous emulsion may be due to the formation of a mechanical barrier of the polymer at the sulphur bituminous interface preventing ;~ .
coalescence of the liquid sulphur particles.
In addition the emission of sulphur gases from the binder is reduced when the polymer is preoent in the mixture.
Suitably the emulsion binder composition contains A
;~ about 40/O by weight of sulphur and about 6 0% by weight of ~-~ bituminouis material. Preferably the sulphur content should not !
be less than 20% and not exceed about 50YO by weight of the ~'~ binder and more preferably should be from about 30 to 40YO of .. ..
~ the binder. Thè content of bituminous material is suitably ~ ~
.. . .
~; 50 to 80%~ preferably 60 to 7~/o, by weight, of the binder.
Generally the ratio of sulphur to bituminous material in the ~ ;
~; emulsion will not exceed 1:1 and is preferably within the range 43:100 to 67:100.
The paving mixture suitably contains from about 85%
-' to 95% by weight of mineral aggregate and 5% to 15% by weight .
~ - 3 _ ~
104521~5 of the binder composition; it will be appreciated that the preferred amounts of the ingredients of the paving mixture com~
, `~ position will be governed by aggregate type and gradation in l any particular case.
`'~`'`' .
~ The organosiloxane polymer is employed in an amount `;`, effective to stabilize the emulsion of sulphur in bituminous material. This amount should be effective to prevent any significant sedimentation of liquid sulphur from the emulsion ., ~ when it is maintained at a temperature of 125C to 145C under ``; 10 gentle agitation.
Suitably the amount of organosiloxane polymer will not exceed 0.1%, by weight, based on the weight of bituminous ~, material, and generally amounts of the order of 0.001%, by weight, produce the desired stabilization of the emulsion.
: :.
The bituminous materials employed in this invention are bitumen-containing mixtures such as occur in the native -state and as a residue from petroleum distillation a parti-cularly preferred bituminous material is asphalt.
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The asphalts employed in the invention should be fluid at the temperatures employed.' . Asphalt has a penetration value for paving of from ~$
::; .
.. . :
., : 3 '~ ` ' ' i ', '' ' : ~' ~s ,, 1045265 about 40 to 400, the penetration grade selected for a specific situation being governed largely by the climatic conditions experienced in the particular area to be paved.
~ The organosiloxane polymer is a liquid having the ;~ general formula ~'1 ;~ CH3 CH3 CH3 1 fH3 :' CH3-SIio - -Si-o-~i-o t ~i CH3 H3 Rl R2 In CH3 ~ . , ... .
where n ranges from 0 to 1000and Rl and R2 which may be the same or different are selected from the group consisting of alkyl of 1 to 6 carbon atoms, phenyl, benzyl, phenoxy and halo-alkyl of 1 to 6 carbon atoms, for example, CH3, C6H5, or C3F3H4. me preferred polymers are fluid poly-dimethyl siloxanes having the general formula (CH3)3 SlO [sio- (CH3)2] n- Si (CH3)3 where n ranges from 0 to 2000 and particularly suitable are such siloxanes having a viscosity in the range from about 50 to about 40,000 centistokes, preferably 300 to 12,500 and most preferably of the order of 1000 centistokes at 25C.
As the mineral aggregate, there may be employed any of the aggregates conventionally used in bituminous paving `~
mixtures, as well as synthetic aggregates. Other aggregates considered marginal for conventional paving aggregates may also ~ -be used.
e binder compositions of the invention may be pre-pared by emulsifying the components, the bituminous material being in a fluid - or liquid state and the sulphur being in a molten state, in the preferred amounts described above, in a mixer; the organosiloxane polymer and bituminous material are suitably pre-mixed in a suitable fashion. Any type of convention-_ 5 _ , . . .
... , ., . .. . . ~ . -la4s26s al mixer for producing emulsions may be used, for example a collold mill. Ilowever, the emulsion is readily generated enabling simpler mixing devices to be used. The preferred mixer is a stainless steel Kenics* 5tatic ~ixer which is a simple in-line mixer having no moving parts, mixing being achieved by simultaneous flow division and radial mixing.
The mixing temperature should be in the range where sulphur is in a molten, pumpable state and consequently should be above the melting point of sulphur, about 118-119C, the upper mixing limit is about 159C, above this temperature the sulphur viscosity increases rapidly by several orders of magnitude and it can no longer be pumped. The preferred mixing temperature is in the range 130C to 150C.
To store the emulsion, it is transferred to a thermo-statically controlled vessel maintained at 125C to 145C, where the emulsion is subjected to continuous gentle agitation by for example slowly rotating low pitch propellers or a cir-culating pump. The emulsion can be stored under these conditions, ready for use as the binder in the formation of a paving com-position.
Alternatively, the separate components of the binder composition can be introduced directly and simultaneously into a mixer with the mineral aggregate, and mixed under the con-ditions indicated above for the emulsion formation, in this case a pugmill is particularly suitable as the mixerO
In order to minimize the modifications of existing paving plants and maintain the plants' normal production capacity, it will generally be desirable to join the molten sulphur stream and that comprising the bituminous material plus organosiloxane polymer just prior to the plant weigh bucket. This can be most effectively achieved, and the emulsion generated at the same time by joining the streams and passing ., ' .
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., . ' .
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:, them through a Kenics* Static Mixer of suitable size upstream from the weigh bucket.
The size of the mixer is governed largely by the ` required fluid velocity of the sulphur/bituminous material .:
composition through the mixer and is suitably in the range of about 1 to about 25 ft./sec., preferably of the order of 10 ft./sec.
The binder compositions of the invention are found to have improved storage characteristics as compared with the -~ 10 known sulphur-asphalt binders and exhibit reduced emissions ., .:
- of sulphur gases. Good binder characteristics were demonstrated ~ when the paving compositions were evaluated according to the ;,, Marshall Mix Method ASTM D1559. The binder composition further ~ showed good results in freeze-thaw and immersion compression :~
` tests performed to evaluate adhesive properties of the binder . .~ .
S composition in comparison with conventional paving grade -~ asphalt cement.
i Aging studies indicate that sulphur/asphalt emulsion ~ concretes of the invention exhibit increased durability com-- 20 pared to ordinary asphalt concretes. Computer pavement analyses using the CHEVSL program indicate that savings in asphalt con-` crete layer thickness, and hence savings in materials costs, can be made using the sulphur/asphalt emulsion concretes of the invention.
~ Marshall stability tests on fresh sulphur-asphalt j concretes of the invention show similar values as for comparable asphaltic concretes, however, on curing for a period of two weeks , , substantial increases are observed in the Marshall Stability of .-~ .
s the sulphur asphalt emulsion concretes without an accompanying ;, 30 detrimental decrease in the Marshall Flow. No change in Marshall I Stability with time i3 observed with regular asphaltic concretes.
:. . .
~ A particularly important aspect of the binder com-.^', .
* trademark _ 7 -.. , .. . . , - , ~ -.. . . . ..
~045265 ~ positions of the invention is that the sulphur exhibits "super-,., cooling" i.e. remains liquid below its melting point. Thus paving mixes containing the sulphur asphalt emulsions as the binder retain their workability to lower temperatures than do those containing regular asphalt binders, with resultant advan-tages which will be apparent to one skilled in the art.
The invention is illustrated by reference to the ; following examples which are not to be construed as limiting.
Example 1 The following ingredients were introduced to a total of 1800 gms into a mixer and emulsified at a temperature of '!`' 130C for 10 minutes. ;
:, Liquid sulphur 37.5% by weight Liquid asphalt (Gulf AC500)* 62.5% by weight Dow Corning 200 Fluid ~ - (trademark for a polydimethyl siloxane) 0.001% (based on the weight of asphalt) ~ A control was run without the silicone.
,3 20 The mixer was a Cowles* Dissolver, Model IVG with a `~$ Cowles* Hi-Shear Impeller No. B-1530 (3 in. diameter) operating ~ . .
at a speed of 4400 rpm. The resulting emulsion was degassed to remove entrained air, and separate samples of the emulsion were stored at 130C with mild agitation (propeller rotating at 100-125 rpm). Density measurements were made at the top (T) and bottom (B) of three samples to determine whether or not , settling was occurring and the results are shown in Table I.
;
trademark 8 _ ;. .
: ~ 104S~65 :~.
TABLE I
` Sample 1/2 hr. 5 hr. 72 hr.
B T B T B
Control 1.19 1.05 1.05 1.18 1.80 1.80 Dow Corning*
200 1.19 1.10 1.15 1.19 1.21 1.20 : ,...
-~, The control emulsion had broken within 5 hrs by ~,~ 10 sedimentation of sulphur as shown by the significant variation ` in density between the top of each sample and the bottom, whereas the composition of the invention was essentially un-. ~
changed after 72 hrs. of heated storage. ~ ~;
;~, Example 2 ~ -~`i A molten sulphur stream and one containing asphalt -:5 (Gulf AC500* pen 150 - 200) plus Dow Corning* 200 Fluid (0.001%
by weight of the asphalt) were combined and pumped through a ~ Kenics* Model 1/2-10-320-0 Static Mixer. This is a one-half :.$ . :
inch diameter mixer containing six helical baffles. Fluid i, 20 stream temperatures were maintained at 138C. The linear velocity through the mixer was varied from 0.2 to 2.3 ft./sec.
~' and the sulphur content varied between 15% and 85% by weight I ;
of the asphalt. Samples of the emulsion prepared in this way ~ -,~ were examined for particle size distribution by a photomicro-graphic technique. In all cases the average particle size was ~ ;
less-than 5 microns and the particle size distribution range was narrow.
Example 3 Paving mixes were prepared by the simultaneous inject-ions of liquid sulphur and asphalt cement containing Dow Corning*
200 Fluid into a heated aggregate in a Hobart Laboratory Mixer.
The mixing temperature was 138C and the mixing cycle was 60 ;,~
;'~ * trademark _ 9 _ :, -.i;,~:, - . , . : : - .
seconds. The mix composition was as follows:
Asphalt Cement (Gulf AlC55020~)netratin 4.5 parts by weight ' Liquid Sulphur 3.0 parts by weight Dow Corning* 200 Fluid .001% by weight of the asphalt Aggregate (well graded 3/8") 92.5 parts by weight A control mix containing 6.5 parts of asphalt and no sulphur was prepared and also a mix where the sulphur and asphalt had been pre-emulsified in a Kenics* Static Mixer. The samples were evaluated using the Marshall Method. The asphalt ,' control'was compacted at 127C and 35 blows/face were applied '~, whereas the emulsion samples were compacted at 121C and 30 blows/face. The results are shown in Table II.
TAsLE II
Sample Type Marshall Stability - lbs. Flow - 0.01 ins.
~, 24 hrs. 14 days 24 hrs. 14 days after after afber after _ moldin~ moldinq moldina moldina S.A. 2050 3420 9.5 12.5 '~ S.A. pre-emulsified 2690 4250 9.0 11.0 ; Control 2050 2050 12.0 12.0 , SoA. denotes sulphur-asphalt emulsion of the invention.
The initial compaction temperature of 121C for the sulphur-asphalt samples ensures that the temperature of the , sample will fall below the melting point of sulphur during compaction. If solidification of the sulphur occurs during 30 compaction the samples will loose compactability and this will be reflected in the lower densities and Marshall,stabilities. The data in Table II indicates that freezing has not occurred during, compaction. Although the sulphur-asphalt sample which was not pre-, emulsified had a somewhat lower Marshall stability compared to the pre-emulsified sample, the 24 hr. value was quite high and !
', * trademark _ 10 _ ... . . . .
.
the characteristic increase in -the Marshall Stability was ~i observed over the 14 day period.
Example 4 ' -~ A paving mix was prepared using a 2000 lb. asphalt paving batch plant. The mix composition was as follows:
.
Asphalt Cement (Gulf AC500*
150 - 200 pen) 4.53 parts by weight Sulphur 2.67 parts by weight ; Dow Corning* 200 Fluid 0.001% by weight of the asphalt Aggregate (Well graded ~` 1/2 inch) 92.8 parts by weight The asphalt stream containing the organosiloxane polymer was combined with the molten sulphur stream and passed through a Kenics*, model KMOD-10 mixer. mis is a 1-1/2 inch diameter unit containing six helical elements or baffles. The asphalt and ~ -sulphur were maintained at 138C and the velocity through the -;
-~ mixer was 18 ft./sec. The sulphur-asphalt emulsion was metered ~i; into a pugmill containing the heated aggregate (149C) and the ~
emulsion and aggregate were mixed for 30 seconds. Mix samples -were sub~ected to evaluation by the Marshall Method ASTM D1559;
the results are tabulated in Table III.
i~ TABLE III
; Marshall Stability - lbs. Flow - 0.01 ins.
1 24 hrs. 14 days 24 hrs. 14 days n` after after after after moldin~ moldin~ moldin~ moldin~ _ 2320 3040 9.5 9.5 :J
Example 5 ~, A durability study was aimed at establishing the change , in stiffness of asphaltic concretes containing normal weight and .j lightweight aggregate filler and conventional and sulphur-asphalt emulsion binders.
.`'. , , ~,, * trademark - 11 -. ,~: .
Prior to placing the samples in the test environments, the resillent modulus, MR, and the density of each sample were ~ determined. Samples were placed in a dry environment at each ; of two temperatures, 0F and 140F, for a period of seven months. It has been shown that for ordinary asphaltic concrete, .. .:
storage for seven months at 140F is equivalent to 5 to 7 years .
` aging in terms of recovered asphalt viscosity. The second temper-` ature of 0F was used to determine the MR changes for the low temperature service extreme for asphaltic concretes. The . ~ . . .
~, 10 results are shown in Tables IV and V.
TABLE IV
Sample Type 5 R Final MR Final ~ as %
_I X 10 PSi~ (X 10 PSi)of Oriqinal ~- Emulsion A3.86 2.79 72.3 Asphalt only A 1.29 0.79 61.6 Emulsion B3.90 3.49 89.4 ~~, Asphalt only B 1.13 0~66 58.2 A - denotes a normal weight aggregate j 20 B - denotes a lightweight aggregate "~ Emulsion - denotes a binding formulation of the invention.
":'i ~i TABLE V
~ RESULTS OF STORAGE AT 140F
; Sample Type5 R Final MR Final MR as %
~, (X 10 PSi ) (X 10 psi )_ of Original , , Emulsion A 3.72 4.19 112.7 Asphalt only A 1.26 4.66 370.7 ~-Emulsion B 3.94 5.67 143.9 ~
. .~.
`l Asphalt only B 0.93 3.06 328.5 ~:~
. . .
_12 -- , .
.
,- . :
. , - .
.
Consideration of Table IV qhows that at 0F there is a reduction in the ~ of all the specimens.
, However, the sulphur-asphalt emulsion concrete ` specimens of the invention show a greater retention of strength compared to regular asphalt concretes.
At 140F, Table V, it is clear that the increase in strength of the sulphur-asphalt emulsion concrete specimens is ~ proportionately much less than that for the ordinary asphaltic ;; -`, concrete specimens.
m is indicates less aging (hardening) of the sulphur-asphalt emulsion concretes and suggests better durability ~-properties than their ordinary asphalt counterparts.
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,`~ Compositions comprising sulphur emulsified in asphalt have been proposed as binders in paving compositions in U.S.
- Patent ~o. 2,182,837, however, such binders have not been used to any great extent. These prior binders are of low stability and it is necessary to use them without delay in making pavin:~
compositions, this necessitates manufacturing the binder at `~ the paving plant site, and this in turn requires the use of two mixers, a high shear mixer such as a colloid mill to form an emulsion of sulphur in asphalt, and a pugmill to mix-the minera' -X
aggregates and the emulslon.
,~ In view of the difficulties experienced when using asphalt-sulphur compositions and, until recently, the ready availability of asphalt at low cost, the industry has favoured the use of asphalt alone as a binder for aggregates in paving compositions.
The invention provides an improved binder composition : . . .
~3 having greater stability than the aforementioned prior binder compositions, in which the now readily available sulphur is employed in an emulsion with bituminous material thus reducing the quantity of the more expensive bituminous material employed ~ in the paving mixture. In addition, the invention provides a - 30 simple procedure for manufacturing such emulsions.
The invention further provides a method of manufactur-ing a paving composition which avoids the necessity of a ~,:. ~ ' ' .
~, , - . ~. ~
~045Z65 preliminary mixing operation to form a sulphur-bituminous emulsion.
; It has now been found that a small amount of an organo-siloxane polymer will stabilize an emulsion of sulphur and a bit-. . j uminous material.
According to the invention there is provided a stabilized binder composition for mineral aggregates in the manu-facture of paving mixtures comprising an emulsion of sulphur and a bituminous material and an emulsion stabilizing amount of an organosiloxane polymer in which said bituminous material is a . ~, continuous phase and said sulphur is a dispersed phase.
According to another aspect of the invention there is `~ provided a method of preparing a stabilized binder composition for ~, mineral aggregates in the manufacture of paving mixtures which com-prises mixing together at an elevated temperature bituminous mate-rial, molten sulphur and an emulsion stabilizing amount of a liquid organosiloxane polymer to form an emulsion having a continuous -~ phase of bituminous material and a dispersed phase of molten sul-,~ phur.
.:
In another aspect of the invention there is provided a method of manufacturing a paving composition comprising mineral 1, aggregates and the binder formulation of the inven~ion, which com-/' prises simultaneously mixing together, at an elevated temperature, liquid bituminous material, liquid sulphur, an emul~ion stabilizing amount of an organosiloxane polymer and a major aunt of a mineral aggregate; the sulphur being emulsified in ~ the bituminous material.
,~ In yet another aspect of the invention there is pro-vided a paving composition and a paved surface formed from ~' the paving composition.
In an embodiment of the invention a method is provided for the simple plugged flow blending of the bituminous material and sulphur just prior to the pugmill weight bucket, in cases ., ~ 2 -.','.,' ~ ~ . - '' 104SZ65 ; ~
.
where it is desirous to simplify the paving plant modifications necessary, to enable the binder compositions of the invention -. .
to be used to prepare paving compositions, and also to maintain the paving plant capacity.
In the emulsions of the invention, the liquid sulphur ~; - .
forms a discontinuous phase or dispersed phase in the continuous liquid bituminous phase.
Although the inventors do not wish to be limited to , any particular theory, it is thought that the stabilizing effect of the organosiloxane polymer on the sulphur-bituminous emulsion arises from the formation of an insoluble monolayer of the polymer at the liquid interface of the sulphur and bituminous ~$ material; the monolayer resulting in a significant reduction in the sedimentation rate of liquid sulphur particles during storage.
A further stabilizing of the sulphur-bituminous emulsion may be due to the formation of a mechanical barrier of the polymer at the sulphur bituminous interface preventing ;~ .
coalescence of the liquid sulphur particles.
In addition the emission of sulphur gases from the binder is reduced when the polymer is preoent in the mixture.
Suitably the emulsion binder composition contains A
;~ about 40/O by weight of sulphur and about 6 0% by weight of ~-~ bituminouis material. Preferably the sulphur content should not !
be less than 20% and not exceed about 50YO by weight of the ~'~ binder and more preferably should be from about 30 to 40YO of .. ..
~ the binder. Thè content of bituminous material is suitably ~ ~
.. . .
~; 50 to 80%~ preferably 60 to 7~/o, by weight, of the binder.
Generally the ratio of sulphur to bituminous material in the ~ ;
~; emulsion will not exceed 1:1 and is preferably within the range 43:100 to 67:100.
The paving mixture suitably contains from about 85%
-' to 95% by weight of mineral aggregate and 5% to 15% by weight .
~ - 3 _ ~
104521~5 of the binder composition; it will be appreciated that the preferred amounts of the ingredients of the paving mixture com~
, `~ position will be governed by aggregate type and gradation in l any particular case.
`'~`'`' .
~ The organosiloxane polymer is employed in an amount `;`, effective to stabilize the emulsion of sulphur in bituminous material. This amount should be effective to prevent any significant sedimentation of liquid sulphur from the emulsion ., ~ when it is maintained at a temperature of 125C to 145C under ``; 10 gentle agitation.
Suitably the amount of organosiloxane polymer will not exceed 0.1%, by weight, based on the weight of bituminous ~, material, and generally amounts of the order of 0.001%, by weight, produce the desired stabilization of the emulsion.
: :.
The bituminous materials employed in this invention are bitumen-containing mixtures such as occur in the native -state and as a residue from petroleum distillation a parti-cularly preferred bituminous material is asphalt.
.~ .
The asphalts employed in the invention should be fluid at the temperatures employed.' . Asphalt has a penetration value for paving of from ~$
::; .
.. . :
., : 3 '~ ` ' ' i ', '' ' : ~' ~s ,, 1045265 about 40 to 400, the penetration grade selected for a specific situation being governed largely by the climatic conditions experienced in the particular area to be paved.
~ The organosiloxane polymer is a liquid having the ;~ general formula ~'1 ;~ CH3 CH3 CH3 1 fH3 :' CH3-SIio - -Si-o-~i-o t ~i CH3 H3 Rl R2 In CH3 ~ . , ... .
where n ranges from 0 to 1000and Rl and R2 which may be the same or different are selected from the group consisting of alkyl of 1 to 6 carbon atoms, phenyl, benzyl, phenoxy and halo-alkyl of 1 to 6 carbon atoms, for example, CH3, C6H5, or C3F3H4. me preferred polymers are fluid poly-dimethyl siloxanes having the general formula (CH3)3 SlO [sio- (CH3)2] n- Si (CH3)3 where n ranges from 0 to 2000 and particularly suitable are such siloxanes having a viscosity in the range from about 50 to about 40,000 centistokes, preferably 300 to 12,500 and most preferably of the order of 1000 centistokes at 25C.
As the mineral aggregate, there may be employed any of the aggregates conventionally used in bituminous paving `~
mixtures, as well as synthetic aggregates. Other aggregates considered marginal for conventional paving aggregates may also ~ -be used.
e binder compositions of the invention may be pre-pared by emulsifying the components, the bituminous material being in a fluid - or liquid state and the sulphur being in a molten state, in the preferred amounts described above, in a mixer; the organosiloxane polymer and bituminous material are suitably pre-mixed in a suitable fashion. Any type of convention-_ 5 _ , . . .
... , ., . .. . . ~ . -la4s26s al mixer for producing emulsions may be used, for example a collold mill. Ilowever, the emulsion is readily generated enabling simpler mixing devices to be used. The preferred mixer is a stainless steel Kenics* 5tatic ~ixer which is a simple in-line mixer having no moving parts, mixing being achieved by simultaneous flow division and radial mixing.
The mixing temperature should be in the range where sulphur is in a molten, pumpable state and consequently should be above the melting point of sulphur, about 118-119C, the upper mixing limit is about 159C, above this temperature the sulphur viscosity increases rapidly by several orders of magnitude and it can no longer be pumped. The preferred mixing temperature is in the range 130C to 150C.
To store the emulsion, it is transferred to a thermo-statically controlled vessel maintained at 125C to 145C, where the emulsion is subjected to continuous gentle agitation by for example slowly rotating low pitch propellers or a cir-culating pump. The emulsion can be stored under these conditions, ready for use as the binder in the formation of a paving com-position.
Alternatively, the separate components of the binder composition can be introduced directly and simultaneously into a mixer with the mineral aggregate, and mixed under the con-ditions indicated above for the emulsion formation, in this case a pugmill is particularly suitable as the mixerO
In order to minimize the modifications of existing paving plants and maintain the plants' normal production capacity, it will generally be desirable to join the molten sulphur stream and that comprising the bituminous material plus organosiloxane polymer just prior to the plant weigh bucket. This can be most effectively achieved, and the emulsion generated at the same time by joining the streams and passing ., ' .
* trademark _ 6 _ ', .
., . ' .
.~
:, them through a Kenics* Static Mixer of suitable size upstream from the weigh bucket.
The size of the mixer is governed largely by the ` required fluid velocity of the sulphur/bituminous material .:
composition through the mixer and is suitably in the range of about 1 to about 25 ft./sec., preferably of the order of 10 ft./sec.
The binder compositions of the invention are found to have improved storage characteristics as compared with the -~ 10 known sulphur-asphalt binders and exhibit reduced emissions ., .:
- of sulphur gases. Good binder characteristics were demonstrated ~ when the paving compositions were evaluated according to the ;,, Marshall Mix Method ASTM D1559. The binder composition further ~ showed good results in freeze-thaw and immersion compression :~
` tests performed to evaluate adhesive properties of the binder . .~ .
S composition in comparison with conventional paving grade -~ asphalt cement.
i Aging studies indicate that sulphur/asphalt emulsion ~ concretes of the invention exhibit increased durability com-- 20 pared to ordinary asphalt concretes. Computer pavement analyses using the CHEVSL program indicate that savings in asphalt con-` crete layer thickness, and hence savings in materials costs, can be made using the sulphur/asphalt emulsion concretes of the invention.
~ Marshall stability tests on fresh sulphur-asphalt j concretes of the invention show similar values as for comparable asphaltic concretes, however, on curing for a period of two weeks , , substantial increases are observed in the Marshall Stability of .-~ .
s the sulphur asphalt emulsion concretes without an accompanying ;, 30 detrimental decrease in the Marshall Flow. No change in Marshall I Stability with time i3 observed with regular asphaltic concretes.
:. . .
~ A particularly important aspect of the binder com-.^', .
* trademark _ 7 -.. , .. . . , - , ~ -.. . . . ..
~045265 ~ positions of the invention is that the sulphur exhibits "super-,., cooling" i.e. remains liquid below its melting point. Thus paving mixes containing the sulphur asphalt emulsions as the binder retain their workability to lower temperatures than do those containing regular asphalt binders, with resultant advan-tages which will be apparent to one skilled in the art.
The invention is illustrated by reference to the ; following examples which are not to be construed as limiting.
Example 1 The following ingredients were introduced to a total of 1800 gms into a mixer and emulsified at a temperature of '!`' 130C for 10 minutes. ;
:, Liquid sulphur 37.5% by weight Liquid asphalt (Gulf AC500)* 62.5% by weight Dow Corning 200 Fluid ~ - (trademark for a polydimethyl siloxane) 0.001% (based on the weight of asphalt) ~ A control was run without the silicone.
,3 20 The mixer was a Cowles* Dissolver, Model IVG with a `~$ Cowles* Hi-Shear Impeller No. B-1530 (3 in. diameter) operating ~ . .
at a speed of 4400 rpm. The resulting emulsion was degassed to remove entrained air, and separate samples of the emulsion were stored at 130C with mild agitation (propeller rotating at 100-125 rpm). Density measurements were made at the top (T) and bottom (B) of three samples to determine whether or not , settling was occurring and the results are shown in Table I.
;
trademark 8 _ ;. .
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TABLE I
` Sample 1/2 hr. 5 hr. 72 hr.
B T B T B
Control 1.19 1.05 1.05 1.18 1.80 1.80 Dow Corning*
200 1.19 1.10 1.15 1.19 1.21 1.20 : ,...
-~, The control emulsion had broken within 5 hrs by ~,~ 10 sedimentation of sulphur as shown by the significant variation ` in density between the top of each sample and the bottom, whereas the composition of the invention was essentially un-. ~
changed after 72 hrs. of heated storage. ~ ~;
;~, Example 2 ~ -~`i A molten sulphur stream and one containing asphalt -:5 (Gulf AC500* pen 150 - 200) plus Dow Corning* 200 Fluid (0.001%
by weight of the asphalt) were combined and pumped through a ~ Kenics* Model 1/2-10-320-0 Static Mixer. This is a one-half :.$ . :
inch diameter mixer containing six helical baffles. Fluid i, 20 stream temperatures were maintained at 138C. The linear velocity through the mixer was varied from 0.2 to 2.3 ft./sec.
~' and the sulphur content varied between 15% and 85% by weight I ;
of the asphalt. Samples of the emulsion prepared in this way ~ -,~ were examined for particle size distribution by a photomicro-graphic technique. In all cases the average particle size was ~ ;
less-than 5 microns and the particle size distribution range was narrow.
Example 3 Paving mixes were prepared by the simultaneous inject-ions of liquid sulphur and asphalt cement containing Dow Corning*
200 Fluid into a heated aggregate in a Hobart Laboratory Mixer.
The mixing temperature was 138C and the mixing cycle was 60 ;,~
;'~ * trademark _ 9 _ :, -.i;,~:, - . , . : : - .
seconds. The mix composition was as follows:
Asphalt Cement (Gulf AlC55020~)netratin 4.5 parts by weight ' Liquid Sulphur 3.0 parts by weight Dow Corning* 200 Fluid .001% by weight of the asphalt Aggregate (well graded 3/8") 92.5 parts by weight A control mix containing 6.5 parts of asphalt and no sulphur was prepared and also a mix where the sulphur and asphalt had been pre-emulsified in a Kenics* Static Mixer. The samples were evaluated using the Marshall Method. The asphalt ,' control'was compacted at 127C and 35 blows/face were applied '~, whereas the emulsion samples were compacted at 121C and 30 blows/face. The results are shown in Table II.
TAsLE II
Sample Type Marshall Stability - lbs. Flow - 0.01 ins.
~, 24 hrs. 14 days 24 hrs. 14 days after after afber after _ moldin~ moldinq moldina moldina S.A. 2050 3420 9.5 12.5 '~ S.A. pre-emulsified 2690 4250 9.0 11.0 ; Control 2050 2050 12.0 12.0 , SoA. denotes sulphur-asphalt emulsion of the invention.
The initial compaction temperature of 121C for the sulphur-asphalt samples ensures that the temperature of the , sample will fall below the melting point of sulphur during compaction. If solidification of the sulphur occurs during 30 compaction the samples will loose compactability and this will be reflected in the lower densities and Marshall,stabilities. The data in Table II indicates that freezing has not occurred during, compaction. Although the sulphur-asphalt sample which was not pre-, emulsified had a somewhat lower Marshall stability compared to the pre-emulsified sample, the 24 hr. value was quite high and !
', * trademark _ 10 _ ... . . . .
.
the characteristic increase in -the Marshall Stability was ~i observed over the 14 day period.
Example 4 ' -~ A paving mix was prepared using a 2000 lb. asphalt paving batch plant. The mix composition was as follows:
.
Asphalt Cement (Gulf AC500*
150 - 200 pen) 4.53 parts by weight Sulphur 2.67 parts by weight ; Dow Corning* 200 Fluid 0.001% by weight of the asphalt Aggregate (Well graded ~` 1/2 inch) 92.8 parts by weight The asphalt stream containing the organosiloxane polymer was combined with the molten sulphur stream and passed through a Kenics*, model KMOD-10 mixer. mis is a 1-1/2 inch diameter unit containing six helical elements or baffles. The asphalt and ~ -sulphur were maintained at 138C and the velocity through the -;
-~ mixer was 18 ft./sec. The sulphur-asphalt emulsion was metered ~i; into a pugmill containing the heated aggregate (149C) and the ~
emulsion and aggregate were mixed for 30 seconds. Mix samples -were sub~ected to evaluation by the Marshall Method ASTM D1559;
the results are tabulated in Table III.
i~ TABLE III
; Marshall Stability - lbs. Flow - 0.01 ins.
1 24 hrs. 14 days 24 hrs. 14 days n` after after after after moldin~ moldin~ moldin~ moldin~ _ 2320 3040 9.5 9.5 :J
Example 5 ~, A durability study was aimed at establishing the change , in stiffness of asphaltic concretes containing normal weight and .j lightweight aggregate filler and conventional and sulphur-asphalt emulsion binders.
.`'. , , ~,, * trademark - 11 -. ,~: .
Prior to placing the samples in the test environments, the resillent modulus, MR, and the density of each sample were ~ determined. Samples were placed in a dry environment at each ; of two temperatures, 0F and 140F, for a period of seven months. It has been shown that for ordinary asphaltic concrete, .. .:
storage for seven months at 140F is equivalent to 5 to 7 years .
` aging in terms of recovered asphalt viscosity. The second temper-` ature of 0F was used to determine the MR changes for the low temperature service extreme for asphaltic concretes. The . ~ . . .
~, 10 results are shown in Tables IV and V.
TABLE IV
Sample Type 5 R Final MR Final ~ as %
_I X 10 PSi~ (X 10 PSi)of Oriqinal ~- Emulsion A3.86 2.79 72.3 Asphalt only A 1.29 0.79 61.6 Emulsion B3.90 3.49 89.4 ~~, Asphalt only B 1.13 0~66 58.2 A - denotes a normal weight aggregate j 20 B - denotes a lightweight aggregate "~ Emulsion - denotes a binding formulation of the invention.
":'i ~i TABLE V
~ RESULTS OF STORAGE AT 140F
; Sample Type5 R Final MR Final MR as %
~, (X 10 PSi ) (X 10 psi )_ of Original , , Emulsion A 3.72 4.19 112.7 Asphalt only A 1.26 4.66 370.7 ~-Emulsion B 3.94 5.67 143.9 ~
. .~.
`l Asphalt only B 0.93 3.06 328.5 ~:~
. . .
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.
,- . :
. , - .
.
Consideration of Table IV qhows that at 0F there is a reduction in the ~ of all the specimens.
, However, the sulphur-asphalt emulsion concrete ` specimens of the invention show a greater retention of strength compared to regular asphalt concretes.
At 140F, Table V, it is clear that the increase in strength of the sulphur-asphalt emulsion concrete specimens is ~ proportionately much less than that for the ordinary asphaltic ;; -`, concrete specimens.
m is indicates less aging (hardening) of the sulphur-asphalt emulsion concretes and suggests better durability ~-properties than their ordinary asphalt counterparts.
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Claims (20)
1. A stabilized binder composition for mineral aggregates in the manufacture of paving mixtures comprising an emulsion of sulphur and a bituminous material and an emulsion stabilizing amount of an organosiloxane polymer; of the general formula:
where n ranges from 0 to 1000 and R1 and R2 which may be the same or different are selected from the group consisting of alkyl of 1 to 6 carbon atoms, phenyl, phenoxy, benzyl and halo-alkyl of 1 to 6 carbon atoms, in which said bituminous material is a continuous phase and said sulphur is a dispersed phase,
where n ranges from 0 to 1000 and R1 and R2 which may be the same or different are selected from the group consisting of alkyl of 1 to 6 carbon atoms, phenyl, phenoxy, benzyl and halo-alkyl of 1 to 6 carbon atoms, in which said bituminous material is a continuous phase and said sulphur is a dispersed phase,
2. A composition according to claim 1, in which said polymer has the formula where n ranges from 0 to 2000 and is selected such that the polymer has a viscosity of about 300 to 12,500 centistokes at 25°C.
3, A composition according to claim 1 or 2 comprising 60 to 70%, by weight, of said bituminous material and 30 to 40%
by weight, of said sulphur based on the weight of said composition; and not more than 0.1%, by weight, of said polymer, based on the weight of said bituminous material.
by weight, of said sulphur based on the weight of said composition; and not more than 0.1%, by weight, of said polymer, based on the weight of said bituminous material.
4. A composition according to claim 1 or 2 comprising 50 to 80%, by weight, of said bituminous material and 20 to 50%, by weight of said sulphur, based on the weight of said composition.
5. A composition according to claim 1 or 2, wherein said bituminous material is asphalt comprising 60 to 70%, by weight, of said asphalt and 30 to 40% by weight of said sulphur based on the weight of said composition and wherein said polymer is present in a stabilizing amount of about 0.001%, by weight, based on the weight of asphalt.
6. A paving mix suitable for forming a paved surface comprising from about 85% to 95%, by weight, of mineral aggregate and from 5% to 15%, by weight, of a binder com-position; said binder composition comprising an emulsion having a continuous phase of a bituminous material and a dispersed phase of sulphur and containing an emulsion stabilizing amount of an organosiloxane polymer of the general formula:
where n ranges from 0 to 1000 and R1 and R2 which may be the same or different are selected from the group consisting of alkyl of 1 to 6 carbon atoms, phenyl, phenoxy, benzyl and halo alkyl of 1 to 6 carbon atoms.
where n ranges from 0 to 1000 and R1 and R2 which may be the same or different are selected from the group consisting of alkyl of 1 to 6 carbon atoms, phenyl, phenoxy, benzyl and halo alkyl of 1 to 6 carbon atoms.
7. A paving mix according to claim 6, in which said binder composition comprises 60 to 70%, by weight, of said bituminous material and 30 to 40%, by weight, of said sulphur based on the weight of said composition; and not more than 0.1% by weight, of said polymer, based on the weight of said bituminous material.
8. A paving mix according to claim 7 wherein said bituminous material is asphalt and said polymer is present in a stabilizing amount of about 0.001%, by weight, based on the weight of asphalt.
9. A paving mix according to claim 6, 7 or 8 in which said polymer has the formula where n ranges from 0 to 2000 and is selected such that the polymer has a viscosity of about 300 to about 12,500 centistokes at 25°C.
10. A paved surface formed from a paving mix according to claim 6, 7 or 8.
11. A method of preparing a stabilized binder composition for mineral aggregates in the manufacture of paving mixtures which comprises mixing together at an elevated temperature not higher than about 159°C, bituminous material, molten sulphur and an emulsion stabilizing amount of a liquid organosiloxane polymer to form an emulsion having a continuous phase of bituminous material and a dispersed phase of molten sulphur said polymer having the general formula:
where n ranges from 0 to 1000 and R1 and R2 which may be the same or different are selected from the group consisting of alkyl of 1 to 6 carbon atoms, phenyl, phenoxy, benzyl and halo alkyl of 1 to 6 carbon atoms.
where n ranges from 0 to 1000 and R1 and R2 which may be the same or different are selected from the group consisting of alkyl of 1 to 6 carbon atoms, phenyl, phenoxy, benzyl and halo alkyl of 1 to 6 carbon atoms.
12. A method according to claim 11, in which the ingredients are mixed to form an emulsion containing 60 to 70%, by weight, of said bituminous material and 30 to 40%, by weight, of said sulphur based on the weight of said com-position; and not more than 0.1%, by weight, of said polymer, based on the weight of said bituminous material,
13. A method according to claim 12, in which said polymer has the formula where n ranges from 0 to 2000 and is selected such that the polymer has a viscosity of about 300 to about 12,500 centistokes at 25°C.
14. A method according to claim 11, 12 or 13 wherein said mixing is at a temperature of from about 130°C to about 150°C.
15. A method according to claim 11, 12 or 13, including maintaining the resulting emulsion in a thermo-statically controlled storage vessel at a temperature of 125°C
to 145°C under gentle agitation.
to 145°C under gentle agitation.
16. A method according to claim 11, wherein the ingredients of the composition are passed through an in-line static mixer having a plurality of baffles adapted to produce flow division and radial mixing of the composition, said bituminous material and sulphur being combined at a point immediately prior to said mixer.
17. A method according to claim 16 wherein said ingredients flow through said static mixer with a fluid stream velocity in the range of 1 to 25 ft/sec.
18. A method of preparing a bituminous paving mixture comprising mixing at an elevated temperature not higher than about 159°C. a major amount of a mineral aggregate, a liquid bituminous material, liquid sulphur and an emulsion stabilizing amount of an organosiloxane polymer of the general formula:
where n ranges from 0 to 1000 and R1 and R2 which may be the same or different are selected from the group consisting of alkyl of 1 to 6 carbon atoms, phenyl, phenoxy, benzyl and halo alkyl of 1 to 6 carbon atoms, such that said liquid sulphur is emulsified in said liquid bituminous material.
where n ranges from 0 to 1000 and R1 and R2 which may be the same or different are selected from the group consisting of alkyl of 1 to 6 carbon atoms, phenyl, phenoxy, benzyl and halo alkyl of 1 to 6 carbon atoms, such that said liquid sulphur is emulsified in said liquid bituminous material.
19. A method according to claim 18 wherein said mixing is in a pugmill and said bituminous material containing said polymer and said sulphur are introduced simultaneously into the pugmill containing the mineral aggregate.
20. A method according to claim 19 wherein said bituminous material and said sulphur are introduced into a static mixer having a plurality of baffles adapted to produce flow division and radial mixing, at a point immediately prior to said pugmill.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7536862A FR2293471A1 (en) | 1974-12-03 | 1975-12-02 | Stabilised binding agent for mineral filler - contg. emulsion of sulphur, bitumen and organo siloxane polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB52222/74A GB1503670A (en) | 1974-12-03 | 1974-12-03 | Sulphurbituminous compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1045265A true CA1045265A (en) | 1978-12-26 |
Family
ID=10463097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA240,696A Expired CA1045265A (en) | 1974-12-03 | 1975-11-28 | Sulphur-bituminous compositions stabilized with organosiloxane polymer |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5425937B2 (en) |
| CA (1) | CA1045265A (en) |
| DE (1) | DE2554415C2 (en) |
| GB (1) | GB1503670A (en) |
| IT (1) | IT1051025B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5084577A (en) * | 1988-03-16 | 1992-01-28 | The Procter & Gamble Company | Volatile silicon compounds |
| US5002762A (en) * | 1988-03-16 | 1991-03-26 | The Procter & Gamble Company | Volatile silicons in household and cosmetic products |
| JP5188004B2 (en) | 2004-02-17 | 2013-04-24 | 東レ・ダウコーニング株式会社 | Method for producing liquid medium-chain alkyl-modified polydimethylsiloxane product and cosmetics |
-
1974
- 1974-12-03 GB GB52222/74A patent/GB1503670A/en not_active Expired
-
1975
- 1975-11-28 CA CA240,696A patent/CA1045265A/en not_active Expired
- 1975-12-02 IT IT29925/75A patent/IT1051025B/en active
- 1975-12-03 JP JP14455075A patent/JPS5425937B2/ja not_active Expired
- 1975-12-03 DE DE2554415A patent/DE2554415C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51102019A (en) | 1976-09-09 |
| IT1051025B (en) | 1981-04-21 |
| JPS5425937B2 (en) | 1979-08-31 |
| DE2554415A1 (en) | 1976-06-10 |
| GB1503670A (en) | 1978-03-15 |
| DE2554415C2 (en) | 1984-09-13 |
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